Safening composition of 6-(trisubstituted phenyl)-4-amino-2-pyridinecarboxylate herbicides and cloquintocet-mexyl for cereal crops

ABSTRACT

Herbicidal injury caused by 6-(trisubstituted phenyl)-4-amino-2-pyridinecarboxylates in wheat and barley is reduced with the use of low rates of cloquintocet.

FIELD OF THE INVENTION

This application claims the benefit of U.S. Provisional Application Ser.No. 61/117,330 filed on Nov. 24, 2008. This invention concerns thesafening of the herbicidal injury caused by 6-(trisubstitutedphenyl)-4-amino-2-pyridinecarboxylates in cereal crops.

BACKGROUND OF THE INVENTION

When agrochemicals, such as plant protection agents and especiallyherbicides, are used, the cultivated plants may be damaged to a certaindegree, depending on factors such as the dose of agrochemicals and theirmethod of application, the species of cultivated plant, the nature ofthe soil and climatic conditions, for example, length of time ofexposure to light, temperature and amounts of precipitation. Thus, it isknown that cultivated plants which are to be protected from the adverseeffect of undesirable plant growth may be damaged to a certain degreewhen an effective dose of herbicide is used. Various substances whichare capable of specifically preventing the adverse effect of anherbicide on the cultivated plants, i.e. of protecting the cultivatedplants without at the same time noticeably influencing the herbicidalaction on weeds to be combated, have been proposed to solve thisproblem. However, it has been found that the antidotes proposedfrequently have only a narrow field of use, i.e., a particular antidoteis frequently suitable only for use with individual species ofcultivated plants and/or for protecting the cultivated plants fromindividual herbicidal substances or classes of substances. It has alsobeen found that the antidotes proposed frequently are used at rateshigher than the rates of the individual herbicidal substance.

U.S. Pat. No. 7,314,849 B2 describes certain 6-(polysubstitutedaryl)-4-amino-2-pyridinecarboxylate compounds and their use asherbicides. While certain of these compounds have been shown to beparticularly effective herbicides for controlling undesirable vegetationin cereal crops, they have also been shown to produce slight amounts ofdamage to both wheat and barley at concentrations required to adequatelycontrol the undesirable vegetation. U.S. Pat. No. 7,314,849 B2 alsodescribes the safening of the herbicidal injury with cloquintocet-mexylat herbicide-to-safener ratio that lies within the range of betweenabout 1:1 and about 1:4, i.e., at a ratio where the rate of safener isequal to or exceeds the rate of the herbicide.

SUMMARY OF THE INVENTION

It has now been found that, surprisingly, the phytotoxic effect ofcertain 6-(trisubstituted aryl)-4-amino-2-pyridinecarboxylate compounds,which have an auxinic mode of action, on wheat and barley, can beameliorated by the use of quinolinyloxyacetate safeners at very lowrates. The present invention concerns a method of protecting cerealcrops from the harmful effects of a 6-(trisubstitutedphenyl)-4-amino-2-pyridinecarboxylate herbicide of the formula (I)

-   -   wherein hal represents F, Cl or Br, and R represents methyl or        ethyl,        and its agriculturally acceptable salt, ester and amide        derivatives which comprises contacting wheat and barley with, or        applying to the area under cultivation, a safener selected from        the quinolinyloxyacetate family of chemicals in which the weight        ratio of 6-(trisubstituted aryl)-4-amino-2-pyridinecarboxylate        herbicide to quinolinyloxyacetate safener is between about 2:1        to about 64:1. The unexpectedly low rates of        quinolinyloxyacetate prevent the herbicidal effects of a        6-(trisubstituted phenyl)-4-amino-2-pyridinecarboxylate        herbicide of the formula (I) on cereal crops such as wheat and        barley.

The present invention also concerns a composition for protecting wheatand barley from the harmful effects of a 6-(trisubstitutedphenyl)-4-amino-2-pyridinecarboxylate herbicide of the formula (I)

-   -   wherein hal represents F, Cl or Br, and R represents methyl or        ethyl,        and its agriculturally acceptable salt, ester and amide        derivatives which comprises, in addition to the        6-(trisubstituted phenyl)-4-amino-2-pyridinecarboxylate        herbicide, an active safener from the quinolinyloxyacetate        family of chemicals in which the weight ratio of        6-(trisubstituted aryl)-4-amino-2-pyridinecarboxylate herbicide        to quinolinyloxyacetate safener is between about 2:1 to about        64:1. In preferred compositions, the 6-(trisubstituted        phenyl)-4-amino-2-pyridinecarboxylate herbicide is a        4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-2-pyridinecarboxylic        acid derivative or a        4-amino-3-chloro-6-(2,4-dichloro-3-methoxyphenyl)-2-pyridinecarboxylic        acid derivative. In preferred compositions, the        quinolinyloxyacetate safener is cloquintocet, most preferably        cloquintocet-mexyl.

It has been surprisingly found that the use of cloquintocet-mexyl at lowrates in composition with a pyridinecarboxylate herbicide of the formula(I) exhibits a protecting effect against the phytotoxicity of thepyridinecarboxylate herbicide of formula (I) on spring and winter wheat(Triticum aestivum L; TRZAS, TRZAW), durum wheat (Triticum durum L;TRZDU) and spring and winter barley (Hordeum vulgare L; HORVS, HORVW) atherbicide-to -safener ratios between 2:1 and 64:1 without losing theherbicidal effects on weeds such as cleavers (Galium aparine L; GALAP),purple deadnettle (Lamium purpureum L; LAMPU), kochia (Kochia scopariaL; KCHSC), scented mayweed (Matricaria chamomila L; MATCH), corn poppy(Papaver rhoeas L; PAPRH), wild buckwheat (Polygonum convolvulus L;POLCO), Russian thistle (Salsola iberica L; SASKR), chickweed (Stellariamedia L; STEME), bird's-eye speedwell (Veronica persica L; VERPE), wildpansy (Viola tricolor L; VIOTR).

DETAILED DESCRIPTION OF THE INVENTION

The pyridinecarboxylic acids of formula I are a new class of compoundshaving herbicidal activity. A number of pyridinecarboxylic acidcompounds are described in U.S. Pat. No. 7,314,849 B2, including4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-pyridine-2-carboxylicacid. The pyridinecarboxylic acids of formula (I) control annual grassweeds and broadleaf weeds in wheat and barley but can be phytotoxic towheat and barley at commercially herbicidal doses.

Safeners from the quinolinyloxyacetate family of chemicals are describedin U.S. Pat. No. 4,902,340. The preferred safeners from thequinolinyloxyacetate family of chemicals are derivatives ofcloquintocet, most preferably the mexyl ester. Cloquintocet is thecommon name for [(5-chloro-8-quinolinyl)oxy]acetic acid. Its safeningactivity is described in The Pesticide Manual, Fourteenth Edition, 2006.Cloquintocet is used as a safener in small grain cereals.

The term herbicide is used herein to mean an active ingredient thatkills, controls or otherwise adversely modifies the growth of plants. Anherbicidally effective or vegetation controlling amount is an amount ofactive ingredient which causes an adversely modifying effect andincludes deviations from natural development, killing, regulation,desiccation, retardation, and the like. The terms plants and vegetationinclude germinant seeds, emerging seedlings and established vegetation.The term safener, as used herein, refers to a compound that selectivelyprotects crop plants from herbicide damage without significantlyreducing activity in target weed species.

Herbicidal activity is exhibited by the compounds when they are applieddirectly to the plant or to the locus of the plant via foliar, soil, orwater application at any stage of growth or before planting oremergence. The effect observed depends upon the plant species to becontrolled, the stage of growth of the plant, the application parametersof dilution and spray drop size, the particle size of solid components,the environmental conditions at the time of use, the specific compoundemployed, the specific adjuvants and carriers employed, the soil type,and the like, as well as the amount of chemical applied. These and otherfactors can be adjusted as is known in the art to promote non-selectiveor selective herbicidal action. Generally, it is preferred to apply thecomposition of the present invention postemergence to relativelyimmature undesirable vegetation to achieve the maximum control of weeds.

Cultivated plants which are to be protected from the adverse effect ofundesirable plant growth may be damaged to a certain degree when aneffective dose of herbicides is used. Safening means preventing theadverse effect of an herbicide on the cultivated plants, i.e.,protecting the cultivated plants without, at the same time, noticeablyinfluencing the herbicidal action on weeds to be combated.

In the composition of this invention, the weight ratio of thepyridinecarboxylic acid of formula (I) to the safener at which theherbicidal effect on the cultivated plant is prevented lies within therange of between about 2:1 and about 64:1. Preferably, the weight ratioof the pyridinecarboxylic acid of formula (I) to the safener at whichthe herbicidal effect on the cultivated plant is prevented lies withinthe range of between about 4:1 and about 32:1.

The rate at which the safened composition is applied will depend uponthe particular type of weed to be controlled, the degree of controlrequired, and the timing and method of application. In general, thecomposition of the invention can be applied at an application rate ofbetween about 0.8 grams per hectare (g/ha) and about 350 g/ha based onthe total amount of pyridinecarboxylic acid of formula (I) and safenerin the composition. In an especially preferred embodiment of theinvention, cloquintocet is applied at a rate between about 0.273 g/haand about 70 g/ha and the pyridinecarboxylic acid of formula (I)component is applied at a rate between about 0.55 g/ha and about 280g/ha.

The pyridinecarboxylic acid of formula (I) and the safener of thepresent invention can be applied either separately or together as partof a multipart herbicidal system.

The herbicide-safener mixture of the present invention can be applied inconjunction with one or more other herbicides to control a wider varietyof undesirable vegetation. When used in conjunction with otherherbicides, the composition can be formulated with the other herbicideor herbicides, tank mixed with the other herbicide or herbicides orapplied sequentially with the other herbicide or herbicides. Some of theherbicides that can be employed in conjunction with the safenedcomposition of the present invention include: 2,4-D esters and amines,acetochlor, acifluorfen, aclonifen, AE0172747, alachlor, amidosulfuron,aminocyclopyrachlor, aminotriazole, ammonium thiocyanate, anilifos,atrazine, AVH 301, azimsulfuron, benfuresate, bensulfuron-methyl,bentazone, benthiocarb, benzobicyclon, bifenox, bispyribac-sodium,bromacil, bromoxynil, butachlor, butafenacil, butralin, cafenstrole,carbetamide, carfentrazone-ethyl, chlorflurenol, chlorimuron,chlorpropham, cinosulfuron, clethodim, clomazone, clopyralid,cloransulam-methyl, cyclosulfamuron, cycloxydim, cyhalofop-butyl,dicamba, dichlobenil, dichlorprop-P, diclosulam, diflufenican,diflufenzopyr, dimethenamid, dimethenamid-p, diquat, dithiopyr, diuron,EK2612, EPTC, esprocarb, ET-751, ethoxysulfuron, ethbenzanid, F7967,fenoxaprop, fenoxaprop-ethyl, fenoxaprop-ethyl+isoxadifen-ethyl,fentrazamide, flazasulfuron, florasulam, fluazifop, fluazifop-P-butyl,flucetosulfuron, flufenacet, flufenpyr-ethyl, flumetsulam,flumiclorac-pentyl, flumioxazin, fluometuron, flupyrsulfuron,fluoroxypyr, fomesafen, foramsulfuron, fumiclorac, glufosinate,glufosinate-ammonium, glyphosate, halosulfuron, haloxyfop-methyl,haloxyfop-R, imazamethabenz, imazamox, imazapic, imazapyr, imazaquin,imazethapyr, imazosulfuron, indanofan, iodosulfuron, ioxynil, IR 5790,isoproturon, isoxaben, isoxaflutole, KUH-021, lactofen, linuron, MCPA,MCPA ester & amine, mecoprop-P, mefenacet, mesosulfuron, mesotrione,metamifop, metolachlor, metosulam, metribuzin, metsulfuron, molinate,MSMA, napropamide, nicosulfuron, norflurazon, OK-9701, orthosulfamuron,oryzalin, oxadiargyl, oxadiazon, oxazichlomefone, oxyfluorfen, paraquat,pendimethalin, penoxsulam, pentoxazone, pethoxamid, picloram,picolinafen, piperophos, pretilachlor, profoxydim, propachlor, propanil,propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyrasulfotole,pyrazogyl, pyrazosulfuron, pyribenzoxim, pyriftalid, pyriminobac-methyl,primisulfuron, pyroxsulam, quinclorac, quizalofop-ethyl-D, S-3252,saflufenacil, sethoxydim, simazine, SL-0401, SL-0402, s-metolachlor,sulcotrione, sulfentrazone, sulfosate, tebuthiuron, terbacil, TH-547,thiazopyr, thiobencarb, triclopyr, triclopyr esters and amine,trifluralin and tritosulfuron.

The safened composition of the present invention can, further, be usedin conjunction with glyphosate, glufosinate, dicamba, imidazolinones or2,4-D on glyphosate-tolerant, glufosinate-tolerant, dicamba-tolerant,imidazolinone-tolerant or 2,4-D-tolerant crops. It is generallypreferred to use the herbicide-safener mixture of the present inventionin combination with herbicides that are selective for the crop beingtreated and which complement the spectrum of weeds controlled by thesecompounds at the application rate employed. It is further generallypreferred to apply the safened composition of the present invention andother complementary herbicides at the same time, either as a combinationformulation or as a tank mix.

In practice, it is preferable to use the safened composition of thepresent invention in mixtures containing an herbicidally effectiveamount of the herbicidal components along with at least oneagriculturally acceptable adjuvant or carrier. Suitable adjuvants orcarriers should not be phytotoxic to valuable crops, particularly at theconcentrations employed in applying the compositions for selective weedcontrol in the presence of crops, and should not react chemically withherbicidal components or other composition ingredients. Such mixturescan be designed for application directly to weeds or their locus or canbe concentrates or formulations that are normally diluted withadditional carriers and adjuvants before application. They can besolids, such as, for example, dusts, granules, water dispersiblegranules, or wettable powders, or liquids, such as, for example,emulsifiable concentrates, solutions, emulsions or suspensions.

Suitable agricultural adjuvants and carriers that are useful inpreparing the herbicidal mixtures of the invention are well known tothose skilled in the art. Some of these adjuvants include, but are notlimited to, crop oil concentrate (mineral oil (85%)+emulsifiers (15%));nonylphenol ethoxylate; benzylcocoalkyldimethyl quaternary ammoniumsalt; blend of petroleum hydrocarbon, alkyl esters, organic acid, andanionic surfactant; C₉-C₁₁ alkylpolyglycoside; phosphated alcoholethoxylate; natural primary alcohol (C₁₂-C₁₆) ethoxylate;di-sec-butylphenol EO-PO block copolymer; polysiloxane-methyl cap;nonylphenol ethoxylate+urea ammonium nitrate; emulsified methylated seedoil; tridecyl alcohol (synthetic) ethoxylate (8E0); tallow amineethoxylate (15 EO); PEG(400) dioleate-99.

Liquid carriers that can be employed include water, toluene, xylene,petroleum naphtha, crop oil, acetone, methyl ethyl ketone,cyclohexanone, trichloroethylene, perchloroethylene, ethyl acetate, amylacetate, butyl acetate, propylene glycol monomethyl ether and diethyleneglycol monomethyl ether, methyl alcohol, ethyl alcohol, isopropylalcohol, amyl alcohol, ethylene glycol, propylene glycol, glycerine,N-methyl-2-pyrrolidinone, N,N-dimethyl alkylamides, dimethyl sulfoxide,liquid fertilizers and the like. Water is generally the carrier ofchoice for the dilution of concentrates.

Suitable solid carriers include talc, pyrophyllite clay, silica,attapulgus clay, kaolin clay, kieselguhr, chalk, diatomaceous earth,lime, calcium carbonate, bentonite clay, Fuller's earth, cotton seedhulls, wheat flour, soybean flour, pumice, wood flour, walnut shellflour, lignin, and the like.

It is usually desirable to incorporate one or more surface-active agentsinto the compositions of the present invention. Such surface-activeagents are advantageously employed in both solid and liquidcompositions, especially those designed to be diluted with carrierbefore application. The surface-active agents can be anionic, cationicor nonionic in character and can be employed as emulsifying agents,wetting agents, suspending agents, or for other purposes. Surfactantsconventionally used in the art of formulation and which may also be usedin the present formulations are described, inter alia, in “McCutcheon'sDetergents and Emulsifiers Annual,” MC Publishing Corp., Ridgewood,N.J., 1998 and in “Encyclopedia of Surfactants,” Vol. I-III, ChemicalPublishing Co., New York, 1980-81. Typical surface-active agents includesalts of alkyl sulfates, such as diethanolammonium lauryl sulfate;alkylarylsulfonate salts, such as calcium dodecylbenzenesulfonate;alkylphenol-alkylene oxide addition products, such as nonylphenol-C₁₈ethoxylate; alcohol-alkylene oxide addition products, such as tridecylalcohol-C₁₆ ethoxylate; soaps, such as sodium stearate;alkylnaphthalene-sulfonate salts, such as sodiumdibutyl-naphthalenesulfonate; dialkyl esters of sulfosuccinate salts,such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such assorbitol oleate; quaternary amines, such as lauryl trimethylammoniumchloride; polyethylene glycol esters of fatty acids, such aspolyethylene glycol stearate; block copolymers of ethylene oxide andpropylene oxide; salts of mono and dialkyl phosphate esters; vegetableoils such as soybean oil, rapeseed oil, olive oil, castor oil, sunflowerseed oil, coconut oil, corn oil, cotton seed oil, linseed oil, palm oil,peanut oil, safflower oil, sesame oil, tung oil and the like; and estersof the above vegetable oils.

Other additives commonly used in agricultural compositions includecompatibilizing agents, antifoam agents, sequestering agents,neutralizing agents and buffers, corrosion inhibitors, dyes, odorants,spreading agents, penetration aids, sticking agents, dispersing agents,thickening agents, freezing point depressants, antimicrobial agents, andthe like. The compositions may also contain other compatible components,for example, other herbicides, plant growth regulants, fungicides,insecticides, and the like and can be formulated with liquid fertilizersor solid, particulate fertilizer carriers such as ammonium nitrate, ureaand the like.

The concentration of the active ingredients in the herbicide-safenermixture of the present invention is generally from 0.001 to 98 percentby weight. Concentrations from 0.01 to 90 percent by weight are oftenemployed. In compositions designed to be employed as concentrates, theactive ingredients are generally present in a concentration from 5 to 98weight percent, preferably 10 to 90 weight percent. Such compositionsare typically diluted with an inert carrier, such as water, beforeapplication. The diluted compositions usually applied to weeds or thelocus of weeds generally contain 0.0001 to 1 weight percent activeingredient and preferably contain 0.001 to 0.05 weight percent.

The present compositions can be applied to weeds or their locus by theuse of conventional ground or aerial dusters, sprayers, and granuleapplicators, or irrigation water, and by other conventional means knownto those skilled in the art.

The following examples illustrate the present invention.

Evaluation of Postemergence Herbicidal Safening in Cereal Crops

Seeds of the desired test plant species were planted in Sun GroMetroMix® 306 planting mixture, which typically has a pH of 6.0 to 6.8and an organic matter content of about 30 percent, in plastic pots witha surface area of 103.2 square centimeters (cm²). When required toensure good germination and healthy plants, a fungicide treatment and/orother chemical or physical treatment was applied. The plants were grownfor 7-36 days (d) in a greenhouse with an approximate 14-hour (h)photoperiod which was maintained at about 18° C. during the day and 17°C. during the night. Nutrients and water were added on a regular basisand supplemental lighting was provided with overhead metal halide1000-Watt lamps as necessary. The plants were employed for testing whenthey reached the second or third true leaf stage.

Weighed amounts of esters (methyl) or salts (TEA [triethylammonium],potassium [K]) of4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)pyridine-2-carboxylicacid (Compound 1) were dissolved in a volume of 97:3 volume/volume (v/v)acetone/dimethylsulfoxide (DMSO) to obtain stock solutions. If theexperimental compound did not dissolve readily, the mixture was warmedand/or sonicated. The concentrated stock solutions were diluted with anaqueous mixture of 1.5% v/v of Agri-dex crop oil concentrate to providethe appropriate application rates. Compound requirements are based upona 12 mL application volume at a rate of 187 liters per hectare (L/ha).Stocks solutions of the safeners were prepared following the sameprocedure. Spray solutions of the safeners and experimental compoundmixtures were prepared by adding the appropriate volume of both stocksolutions to the appropriate amount of dilution solution to form a 12 mLspray solution with active ingredients in two-way combinations.Formulated compounds were applied to the plant material with an overheadMandel track sprayer equipped with 8002E nozzles calibrated to deliver187 L/ha over an application area of 0.503 square meters (m²) at a sprayheight of 18 inches (43 centimeters (cm)) above average plant canopy.Control plants were sprayed in the same manner with the solvent blank.

The treated plants and control plants were placed in a greenhouse asdescribed above and watered by sub-irrigation to prevent wash-off of thetest compounds. After 20-22 d, the condition of the test plants ascompared with that of the control plants was determined visually andscored on a scale of 0 to 100 percent where 0 corresponds to no injuryand 100 corresponds to complete kill.

Colby's equation was used to determine the herbicidal effects expectedfrom the mixtures (Colby, S. R. Calculation of the synergistic andantagonistic response of herbicide combinations. Weeds 1967, 15,20-22.).

The following equation was used to calculate the expected activity ofmixtures containing two active ingredients, A and B:Expected=A+B−(A×B/100)

A=observed efficacy of active ingredient A at the same concentration asused in the mixture.

B=observed efficacy of active ingredient B at the same concentration asused in the mixture.

Some of the compounds tested, application rates employed, plant speciestested, and results are given in Table 1 through Table 7.

TABLE 1 Safening Activity of Herbicidal Compositions on Wheat and BarleyApplication Rate (g/ha) Compound Cloquin- Herbicide: I Methyl tocet-Safener HORVS TRZAS TRZAW HORVW GALAP KCHSC MATCH SASKR VERPE VIOTREster mexyl Ratio Ob Ex Ob Ex Ob Ex Ob Ex Ob Ex Ob Ex Ob Ex Ob Ex Ob ExOb Ex 8.75 0 — 22 — 13 — 35 0 — 38 — 43 — 70 0 — — 25 — 140 0 — 42 — 37— 32 — 42 — 100 — 100 — 82 — 91 — 91 — 67 — 0 1.1 — 0 — 0 — 0 — 0 — 0 —0 — 0 — 0 2.2 — 0 — 0 — 0 — 0 — 0 — 0 — 0 — 0 4.4 — 0 — 0 — 0 — 0 — 0 —0 — 0 — 0 8.75 — 0 — 0 — 0 — 0 — 0 — 0 — 0 — 0 17.5 — 0 — 0 — 0 — 0 — 0— 0 — 0 — 0 35 — 0 — 0 — 0 — 0 — 0 — 0 — 0 — 0 — 0 — 0 70 — 0 — 0 — 0 —0 — 0 — 0 — 0 — 0 — 0 — 8.75 1.1  8:1 0 22 1 13 35 1.1 31:1 2 38 3 43 701.1 64:1 2 25 140 2.2 64:1 10 37 140 4.4 32:1 7 37 140 8.75 16:1 0 42 237 100 100 86 82 88 91 93 91 62 67 140 17.5  8:1 0 42 2 37 100 100 89 8289 91 92 91 58 67 140 35  4:1 0 42 3 37 5 32 0 42 100 100 100 100 89 8288 91 91 91 60 67 140 70  2:1 0 42 3 37 5 32 0 42 100 100 100 100 83 8289 91 86 91 40 67

TABLE 2 Safening Activity of Herbicidal Compositions on Wheat and BarleyApplication Rate (g/ha) Compound Cloquintocet- Herbicide: HORVS TRZASKCHSC MATCH SASKR VERPE VIOTR (I) K-salt mexyl Safener Ratio Ob Ex Ob ExOb Ex Ob Ex Ob Ex Ob Ex Ob Ex 8.75 0 25 — 15 — — — — — — 35 0 38 — 43 —— — — — — 70 0 — 11 — — — — — — 140 0 45 — 52 — 100 — 88 — 87 — 87 — 63— 0 1.0937 0 — 0 — 0 — 0 — 0 — 0 — 0 — 0 2.1875 0 — 0 — 0 — 0 — 0 — 0 —0 — 0 4.375 0 — 0 — 0 — 0 — 0 — 0 — 0 — 0 8.75 0 — 0 — 0 — 0 — 0 — 0 — 0— 0 17.5 0 — 0 — 0 — 0 — 0 — 0 — 0 — 0 35 0 — 0 — 0 — 0 — 0 — 0 — 0 — 070 0 — 0 — 0 — 0 — 0 — 0 — 0 — 8.75 1.0937  8:1 2 25 1 15 35 1.0937 32:13 38 2 43 70 1.0937 64:1 0 11 140 2.1875 64:1 8 52 140 4.375 32:1 10 52140 8.75 16:1 2 45 0 52 100 100 91 88 87 87 89 87 50 63 140 17.5  8:1 045 0 52 100 100 89 88 90 87 90 87 50 63 140 35  4:1 0 45 0 52 100 100 8588 90 87 90 87 43 63 140 70  2:1 0 45 0 52 100 100 90 88 88 87 92 87 3863

TABLE 3a Safening Activity of Herbicidal Compositions on Wheat andBarley Application Rate (g/ha) Compound Herbicide: (I) TEA Cloquintocet-Safener HORVS TRZAS TRZAW HORVW TRZDU GALAP KCHSC LAMPU salt mexyl RatioOb Ex Ob Ex Ob Ex Ob Ex Ob Ex Ob Ex Ob Ex Ob Ex 8.75 0 25 — 5 — — — — —— 35 0 23 — 15 — — — — — — 70 0 — 10 — — — — — — 140 0 23 — 27 — 24 — 1510 — 100 — 95 — 98 — 0 1.1 0 — 0 — 0 — 0 — 0 — 0 — 0 — 0 2.2 0 — 0 — 0 —0 — 0 — 0 — 0 — 0 4.4 0 — 0 — 0 — 0 — 0 — 0 — 0 — 0 8.75 0 — 0 — 0 — 0 —0 — 0 — 0 — 0 17.5 0 — 0 — 0 — 0 — 0 — 0 — 0 — 0 35 0 — 0 — 0 — 0 — 0 —0 — 0 — 0 — 0 70 0 — 0 — 0 — 0 — 0 — 0 — 0 — 0 — 8.75 1.1  8:1 3 25 1  535 1.1 31:1 3 23 0 15 70 1.1 64:1 0 10 140 2.2 64:1 6 27 140 4.4 32:1 627 140 8.75 16:1 3 23 0 27 100 95 140 17.5  8:1 1 23 0 27 0 24 0 10 100100 89 95 100 98 140 35  4:1 1 23 0 27 3 24 0 15 0 10 100 100 97 95 10098 140 70  2:1 1 23 0 27 0 24 0 15 0 10 100 100 97 95 100 98

TABLE 3b Safening Activity of Herbicidal Compositions on Wheat andBarley Application Rate (g/ha) Compound Herbicide: (I) TEA Cloquintocet-Safener MATCH PAPRH POLCO SASKR STEME VERPE VIOTR salt mexyl Ratio Ob ExOb Ex Ob Ex Ob Ex Ob Ex Ob Ex Ob Ex 8.75 0 — — — — — — — 35 0 — — — — —— — 70 0 — — — — — — — 140 0 84 — 100 — 100 — 86 — 88 — 89 — 66 — 0 1.10 — 0 — 0 — 0 — 0 — 0 — 0 — 0 2.2 0 — 0 — 0 — 0 — 0 — 0 — 0 — 0 4.4 0 —0 — 0 — 0 — 0 — 0 — 0 — 0 8.75 0 — 0 — 0 — 0 — 0 — 0 — 0 — 0 17.5 0 — 0— 0 — 0 — 0 — 0 — 0 — 0 35 0 — 0 — 0 — 0 — 0 — 0 — 0 — 0 70 0 — 0 — 0 —0 — 0 — 0 — 0 — 8.75 1.1  8:1 35 1.1 32:1 70 1.1 64:1 140 2.2 64:1 1404.4 32:1 140 8.75 16:1 86 84 88 86 89 89 62 66 140 17.5  8:1 83 84 100100 100 100 91 86 95 88 90 89 40 66 140 35  4:1 76 84 100 100 100 100 8786 100 88 90 89 34 66 140 70  2:1 88 84 100 100 100 100 88 86 80 88 8989 29 66

TABLE 4 Safening Activity of Herbicidal Compositions on Wheat and BarleyApplication Rate (g/ha) Compound (I) Methyl Cloquintocet-Herbicide:Safener TRZAS HORVS LAMPU PAPRH ester acid Ratio Ob Ex Ob ExOb Ex Ob Ex 35 0 45 43 100 97 0 0.55 0 — 0 — 0 — 0 — 0 1.1 0 — 0 — 0 — 0— 0 2.2 0 — 0 — 0 — 0 — 0 4.4 0 — 0 — 0 — 0 — 35 0.55 64:1 0 45 2 43 100100 100 97 35 1.1 32:1 0 45 1 43 100 100 100 97 35 2.2 16:1 0 45 0 43100 100 100 97 35 4.4  8:1 0 45 0 43 100 100 99 97

TABLE 5 Safening Activity of Herbicidal Compositions on Wheat and BarleyApplication Rate (g/ha) Compound Cloquintocet- (I) Methyltriisopropylamine Herbicide:Safener TRZAS HORVS LAMPU PAPRH ester saltRatio Ob Ex Ob Ex Ob Ex Ob Ex 35 0 45 43 100 97 0 0.55 0 — 0 — 0 — 0 — 01.1 0 — 0 — 0 — 0 — 0 2.2 0 — 0 — 0 — 0 — 0 4.4 0 — 0 — 0 — 0 — 35 0.5564:1 0 45 2 43 100 100 100 97 35 1.1 32:1 0 45 2 43 100 100 100 97 352.2 16:1 0 45 0 43 100 100 100 97 35 4.4  8:1 0 45 0 43 100 100 100 97

TABLE 6 Safening Activity of Herbicidal Compositions on Wheat and BarleyApplication Rate (g/ha) Compound Cloquintocet- (I) Methyltriethanolamine Herbicide:Safener TRZAS HORVS LAMPU PAPRH ester saltRatio Ob Ex Ob Ex Ob Ex Ob Ex 35 0 45 43 100 97 0 0.55 0 — 0 — 0 — 0 — 01.1 0 — 0 — 0 — 0 — 0 2.2 0 — 0 — 0 — 0 — 0 4.4 0 — 0 — 0 — 0 — 35 0.5564:1 0 45 0 43 100 100 100 97 35 1.1 32:1 0 45 0 43 100 100 100 97 352.2 16:1 0 45 0 43 100 100 100 97 35 4.4  8:1 0 45 0 43 100 100 100 97

TABLE 7 Safening Activity of Herbicidal Compositions on Wheat and BarleyApplication Rate (g/ha) Compound Cloquintocet- (I) Methyl dimethylamineHerbicide:Safener TRZAS HORVS LAMPU PAPRH ester salt Ratio Ob Ex Ob ExOb Ex Ob Ex 35 0 45 43 100 97 0 0.55 0 — 0 — 0 — 0 — 0 1.1 0 — 0 — 0 — 0— 0 2.2 0 — 0 — 0 — 0 — 0 4.4 0 — 0 — 0 — 0 — 35 0.55 64:1 0 45 0 43 100100 100 97 35 1.1 32:1 0 45 0 43 100 100 97 97 35 2.2 16:1 0 45 0 43 100100 99 97 35 4.4  8:1 0 0 43 100 100 99 97 TRZAS = Triticum aestivum(spring wheat) TRZAW = Triticum aestivum (winter wheat) TRZDU = Triticumdurum (durum wheat) HORVS = Hordeum vulgare (spring barley) HORVW =Hordeum vulgare (winter barley) GALAP = Galium aparine (cleavers) KCHSC= Kochia scoparia (kochia) LAMPU = Lamium purpureum (purple deadnettle)Ob = Observed values g/ha = grams per hectare MATCH = Matricariachamomila (scented mayweed) PAPRH = Papaver rhoeas (corn poppy) POLCO =Polygonum convolvulus (wild buckwheat) SASKR = Salsola iberica (Russianthistle) STEME = Stellaria media (common chickweed) VERPE = Veronicapersica (bird's-eye speedwell) VIOTR = Viola tricolor (wild pansy) Ex =Expected values

What is claimed is:
 1. A composition for protecting wheat and barleyfrom the harmful effects of a 6-(trisubstitutedphenyl)-4-amino-2-pyridine-carboxylate herbicide of the formula (I)

wherein hal represents F, Cl or Br, and R represents methyl or ethyl,and its agriculturally acceptable salt, ester and amide derivativeswhich comprises, in addition to the 6-(trisubstitutedphenyl)-4-amino-2-pyridinecarboxylate herbicide, a safener from thequinolinyloxyacetate family of chemicals in which the weight ratio of6-(trisubstituted aryl)-4-amino-2-pyridinecarboxylate herbicide toquinolinyloxyacetate safener is between 2:1 to about 64:1.
 2. Thecomposition of claim 1 in which the 6-(trisubstitutedphenyl)-4-amino-2-pyridinecarboxylate herbicide is a4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-2-pyridinecarboxylicacid derivative or a4-amino-3-chloro-6-(2,4-dichloro-3-methoxyphenyl)-2-pyridinecarboxylicacid derivative.
 3. The composition of claim 1 in which the safener iscloquintocet mexyl.
 4. The composition of claim 1 in which the weightratio of the 6-(trisubstituted phenyl)-4-amino-2-pyridinecarboxylateherbicide to the safener is between 4:1 and 32:1.
 5. The composition ofclaim 1, in which the weight ratio of the 6-(trisubstitutedphenyl)-4-amino-2-pyridinecarboxylate herbicide to the safener is fromgreater than 32:1 to 64:1.
 6. The composition of claim 5, in which thesafener is cloquintocet mexyl.
 7. A method of protecting wheat andbarley from the harmful effects of a 6-(trisubstitutedphenyl)-4-amino-2-pyridinecarboxylate herbicide of the formula (I)

wherein hal represents F, Cl or Br, and R represents methyl or ethyl,and its agriculturally acceptable salt, ester and amide derivativeswhich comprises contacting the wheat and barley with, or applying to thearea under cultivation, a safener selected from the quinolinyloxyacetatefamily of chemicals in which the weight ratio of 6-(trisubstitutedaryl)-4-amino-2-pyridinecarboxylate herbicide to quinolinyloxyacetatesafener is between 2:1 to 64:1.
 8. The method of claim 7, in which theweight ratio of 6-(trisubstituted aryl) -4-amino-2-pyridinecarboxylateherbicide to quinolinyloxyacetate safener is from greater than 32:1 to64:1.
 9. The method of claim 8, in which the safener is cloquintocetmexyl.